Method of stimulating a subterranean formation with non-spherical ceramic proppants

ABSTRACT

Non-spherical particulates are useful in the stimulation of subterranean formations. A proppant pack composed of the non-spherical particulates exhibits greater porosity than a corresponding proppant pack composed of spherical particulates. In addition, the non-spherical particulates exhibit higher conductivity at higher stresses than spherical shaped particulates.

This application is a divisional application of U.S. patent applicationSer. No. 13/457,595 as filed Apr. 27, 2012, which is a continuationapplication of U.S. patent application Ser. No. 13/114,766 as filed May24, 2011, now U.S. Pat. No. 8,186,434, which is a continuationapplication of U.S. patent application Ser. No. 12/013,775, now U.S.Pat. No. 7,950,455.

FIELD OF THE INVENTION

This invention relates to non-spherical well treating particulates andmethods of using such particulates in the treatment of subterraneanformations. In particular, this invention relates to non-spherical welltreating particulates which may be at least partially filled with achemical treatment agent and the use of such particulates in hydraulicfracturing and sand control methods, such as gravel packing, frac packtreatments, etc.

BACKGROUND OF THE INVENTION

Stimulation procedures often require the use of well treating materialshaving high compressive strength. In hydraulic fracturing, suchmaterials must further be capable of enhancing the production of fluidsand natural gas from low permeability formations. In a typical hydraulicfracturing treatment, fracturing treatment fluid containing a solidproppant is injected into the wellbore at high pressures. Once naturalreservoir pressures are exceeded, the fluid induces fractures in theformation and proppant is deposited in the fracture, where it remainsafter the treatment is completed. The proppant serves to hold thefracture open, thereby enhancing the ability of fluids to migrate fromthe formation to the wellbore through the fracture. Because fracturedwell productivity depends on the ability of a fracture to conduct fluidsfrom a formation to a wellbore, fracture conductivity is an importantparameter in determining the degree of success of a hydraulic fracturingtreatment. Choosing a proppant is critical to the success of wellstimulation.

The prior art has been principally focused on the development ofspherical well treating particulates. For example, manufactured ceramicproppants have been reported as requiring a sphericity value of about0.70 or greater. See, for instance, Krumbein et al, Stratiography andSedimentation, W.H. Freeman and Co., 1955. The requirement that welltreatment particulates, such as proppants, be spherical particulates maybe attributed to the perception that spherical particulates achieve thehighest possible conductivity throughout the proppant pack and allow forthe highest permeability for a uniform shape.

Proppants used in the art include sand, glass beads, walnut hulls, andmetal shot as well as resin-coated sands, intermediate strengthceramics, and sintered bauxite; each employed for their ability to costeffectively withstand the respective reservoir closure stressenvironment. The relative strength of these various materials increaseswith their corresponding apparent specific gravity (ASG), typicallyranging from 2.65 for sands to 3.6 for sintered bauxite. Unfortunately,increasing ASG leads directly to increasing degree of difficulty withproppant transport and reduced propped fracture volume, thereby reducingfracture conductivity.

More recently, ultra lightweight (ULW) materials have been used asproppants since they reduce the fluid velocity required to maintainproppant transport within the fracture, which, in turn, provides for agreater amount of the created fracture area to be propped. Such ULWproppants, like conventional heavier proppants, have the capability toeffectively withstand reservoir closure stress environments whileincreasing fracture conductivity. While offering excellent compressivestrength, ULW proppants often soften and loose their compressivestrength especially at high temperature and high pressure downholeconditions. Alternatives have therefore been sought.

Improved well treating particulates have also been sought for use in theprevention of sand grains and/or other formation fines from migratinginto the wellbore. When such migration occurs, such grains and finestypically reduce the rate of hydrocarbon production from the well. Inaddition, such grains and fines can cause serious damage to welltubulars and to well surface equipment.

Gravel packs are often used to control migration of particulates in suchproducing formations. A gravel pack typically consists of a uniformlysized mass of spherical particulates which are packed around theexterior of a screening device. Such screening devices, typicallypositioned in an open hole or inside the well casing, have very narrowopenings which are large enough to permit the flow of formation fluidbut small enough to allow the particulates to pass through. Theparticulates operate to trap, and thus prevent the further migration of,formation sand and fines which would otherwise be produced along withthe formation fluid.

In order to be useful in gravel packing applications, such particulatesmust exhibit high strength and be capable of functioning in lowpermeability formations. While ULW well treating agents have beenproposed for use in gravel packing applications to improve transport,placement, and packing efficiency, concerns exist however that ULWparticulates do not demonstrate the chemical resistance propertiesrequired of particulates for use in gravel packing.

Alternative well treating agents have therefore been sought whichexhibit high compressive strength and which may be used to improvepacking efficiency, transport and placement of proppant in fracturing.It is further desired that such materials be useful in other oilfieldtreatment processes, such as sand control.

In addition, alternative proppants which are capable of increasingfracture width as well as conductivity are desired.

It is further desired that alternative well treatment particulates becapable of providing a chemical treatment agent to the wellbore andformation in order to inhibit deleterious conditions which may typicallydevelop. Oilfield fluids (e.g., oil, gas, and water) are complexmixtures of aliphatic hydrocarbons, aromatics, hetero-atomic molecules,anionic and cationic salts, acids, sands, silts, clays and a vast arrayof other components. The nature of these fluids combined with the severeconditions of heat, pressure, and turbulence to which they are oftensubjected during retrieval, are contributory factors of unwanteddeposition of substances which may be responsible for decreasing thepermeability of the subterranean formation as well as reducing wellproductivity and shortening of the lifetime of production equipment.Such may include paraffin deposition (including the precipitation of waxcrystals), formation of water-in-oil as well as oil-in-water emulsions,gas hydrate formation and corrosion and asphaltene precipitation. Inorder to rid such unwanted deposits and precipitates from wells andequipment, it is necessary to stop the production which is bothtime-consuming and costly.

An especially troublesome unwanted deposits are paraffin hydrocarbonwaxes which tend to precipitate and crystallize at low temperatures,thereby causing oil to lose its fluidity. Over a range of temperatures,these paraffin wax crystals continue to aggregate and may even solidifythe oil. This creates difficulties in transporting the petroleum fuel orcrude oil through flow lines, valves, and pumps. Paraffin wax crystalsare particularly problematic at lower temperatures and in colderclimates where, as the temperature drops and approaches the crude oil'spour point, the transportation of crude oil becomes more difficult. Onceout of solution, paraffin wax crystals often plug flow lines, productiontubing, flow lines, screens and filters.

Various well treatment agents are often used in production wells toprevent the deleterious effects caused by the formation andprecipitation of unwanted materials. For instance, pour pointdepressants and wax crystal modifiers have been used to change thenature of wax crystals that precipitate from the petroleum fuel or crudeoil, thereby reducing the tendency of wax crystals to set into a gel.

It is essential that such well treatment agents be placed into contactwith the oilfield fluids contained in the formation before such fluidsenter the wellbore where deleterious effects are commonly encountered.Several methods are known in the art for introducing such well treatmentagents into production wells. A principal disadvantage of such prior artmethods is the difficulty in releasing the well treatment agent into thewell over a sustained period of time. As a result, treatments mustrepeatedly be undertaken to ensure that the requisite level of welltreatment agent is continuously present in the well. Such treatmentsresult in lost production revenue due to down time.

Treatment methods are therefore sought for introducing well treatmentagents into oil and/or gas wells wherein the well treatment agent may bereleased over a sustained period of time. It is desired that suchmethods not require continuous attention of operators over prolongedperiods.

SUMMARY OF THE INVENTION

Non-spherical particulates are useful in stimulation of subterraneanformations and have particular applicability as proppants in thefracturing of hydrocarbon-bearing formations as well as in sand controloperations. The particulates may be porous or non-porous.

The volume and particle size of the non-spherical particulates may beselected so as to generate a close-packed structure of particulates.Such close-packed particulates significantly reinforce the strength (ormodulus) of the composite. Stresses are transmitted through the packedparticulates in communication with one another. As such, thenon-spherical particulates demonstrate significantly improved stresstolerance.

In a preferred embodiment, the non-spherical particulates have a shapewhich is substantially oblong, elliptical or cylindrical. Suchnon-spherical shapes render higher conductivity at higher stresses thanthose evidenced with spherical shaped particulates. The non-sphericalparticulates have an aspect ratio less than or equal to 5.0:1.0,typically less than or equal to 2.5:1.0.

In some instances, the non-spherical particulates may exhibit greaterpermeability than spherical particulates. The apparent specific gravityof the non-spherical particulates defined herein may be from about 1.0to about 4.0. However, the loose-packed bulk densities containing thenon-spherical particulates may be from about 0.5 g/cm³ to about 2.0g/cm³. The bulk density may be due to a loose-packed structure assumedby the non-spherical particulates.

The non-spherical particulates may be treated with a coating layer orglazing material. Such coating materials may be permeable orsemi-permeable to fluids produced from the wellbore.

Use of the non-spherical particulates renders higher porosity to aproppant pack. For instance, the porosity of a proppant pack having aportion of spherical particulates substituted with non-sphericalparticulates has been seen to exhibit greater porosity at an equivalentbulk volume. The porosity of a proppant pack containing non-sphericalparticulates defined herein may range from about 45 to about 70 percent,more typically in the range of from about 50 to about 60 percent.

In another embodiment, the non-spherical particulates are non-porous andare hollow. Such non-spherical particulates are capable of being atleast partially filled with a chemical treatment agent. For instance,the internal volume of the hollow cylindrical non-porous particulatesmay be up to about 70 percent by volume of the cylindrical proppant.

Suitable chemical treatment agents are those which are water-soluble oroil-soluble. Further such chemical treatments agents may those which arecapable of being released into the formation by heat or mechanicalstress. Suitable materials for such non-porous particulates are ceramicsas well as organic polymeric materials, such as polyolefins.

Suitable chemical treatment agents include scale inhibitors, corrosioninhibitors, paraffin inhibitors, demulsifiers, gas hydrate inhibitors,flocculating agents, asphaltene dispersants as well as mixtures thereof.

BRIEF DESCRIPTION OF THE DRAWINGS

In order to more fully understand the drawings referred to in thedetailed description of the present invention, a brief description ofeach drawing is presented, in which:

FIG. 1 shows conductivity data for proppant packs composed ofnon-spherical particulates including proppant packs composed of mixturesof spherical and non-spherical particulates; and

FIG. 2 compares the permeability differences between proppant packscomposed of non-spherical particulates versus spherical particulates.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The non-spherical particulates defined herein are typically lightweightand exhibit high strength. As such, they find particular applicabilityin stimulation and sand control methods, such as hydraulic fracturingand gravel packing.

The non-spherical particulates are principally used to substantiallyimprove productivity in petroleum and gas production. They areespecially useful at high temperature and high pressure downholeconditions. For instance, the non-spherical particulates may be used attemperatures at least up to about 450° F. and at a downhole pressure ofat least up to about 20,000 psi.

In particular, the non-spherical particulates find particularapplicability in the fracturing of hydrocarbon-bearing formations orwater injection wells since they exhibit substantial improvement inoverall system performance. The non-spherical particulates may beintroduced into the wellbore at concentrations sufficient to achieve apartial monolayer of proppant in the fracture. The non-sphericalparticulates are further ideally suited for use in normal fracture packs(as well as sand control packs).

The non-spherical particulates are further capable of preventing sandgrains and/or other formation fines from migrating into the wellbore insand control applications.

In such applications, at least a portion of the non-sphericalparticulates is placed adjacent the subterranean formation to form afluid-permeable pack. The pack is capable of reducing or substantiallypreventing the passage of formation particles from the subterraneanformation into the wellbore. At the same time, formation fluids from thesubterranean formation are permitted to pass into the wellbore.

The volume and particle size of the non-spherical particulates may beselected so as to generate a close-packed structure of particulates.Such close-packed particulates significantly reinforce the strength (ormodulus) of the composite. Stresses are transmitted through the packedparticulates in communication with one another. As such, thenon-spherical particulates demonstrate significantly improved stresstolerance. In a preferred embodiment, the non-spherical particulateshave a shape which is substantially oblong, elliptical or cylindrical.Such non-spherical shapes render higher conductivity at higher stressesthan those evidenced with spherical shaped particulates. Thenon-spherical particulates have an aspect ratio less than or equal to5.0:1.0, typically less than or equal to 2.5:1.0. The shape of thenon-spherical particulates may be selected based on anticipated downholeconditions including the width of the anticipated fracture. Thenon-spherical particulates deform with stress and yet are sufficientlystrong to be used on their own at high pressures, such as a closurestress in excess of 4,000 psi, when the used in a partial monolayerhydraulic fracturing application.

In some instances, the non-spherical particulates may exhibit greaterpermeability than spherical particulates. The apparent specific gravityof the non-spherical particulates defined herein may be from about 1.0to about 4.0. However, the loose-packed bulk densities containing thenon-spherical particulates may be from about 0.5 g/cm³ to about 2.0g/cm³. The bulk density may be due to a loose-packed structure assumedby the non-spherical particulates.

The non-spherical particulate may be composed of untreated or treatedceramics, inorganic oxides or organic polymeric materials. Suitableparticulates include aluminosilicates, silicon carbide, alumina andother silica-based materials. Further, the non-spherical particulatesmay be a naturally occurring or manufactured or engineered material.Examples of non-natural particulate materials for use in the inventioninclude, but are not limited to, plastics, nylon and porous ceramicparticles, such as fired kaolinitic particles, as well as partiallysintered bauxite. The particulates may further be natural ceramicmaterials, such as lightweight volcanic rocks, like pumice, as well asperlite and other porous “lavas” like porous (vesicular) HawaiianBasalt, Virginia Diabase and Utah Rhyolite. Suitable polymeric materialsfor the non-spherical particulate include thermosetting resins andplastics, such as polystyrene, a styrene-divinylbenzene copolymer, apolyacrylate, a polyalkylacrylate, a polyacrylate ester, a polyalkylacrylate ester, a modified starch, a polyepoxide, a polyurethane, apolyisocyanate, a phenol formaldehyde resin, a furan resin, a melamineformaldehyde resin or a polyamide. Composite materials made from thesepolymeric materials may also be used.

Further acceptable non-spherical particulates may include ground orcrushed shells of nuts such as walnut, pecan, almond, ivory nut, brazilnut, etc.; ground or crushed seed shells (including fruit pits) of seedsof fruits such as plum, peach, cherry, apricot, etc.; ground or crushedseed shells of other plants such as maize (e.g., corn cobs or cornkernals), etc. processed wood materials such as those derived from woodssuch as oak, hickory, walnut, poplar, mahogany, etc. including suchwoods that have been processed by grinding, chipping, or other form ofparticalization. Such materials may be chipped, ground, crushed, orotherwise processed to produce the non-spherical particulate material.

In addition to being combined with spherical particulates, a mixture oftwo or more non-spherical particulates (with or without sphericalparticulates) may further be used.

A coating, which may be permeable or semi-permeable to fluids producedfrom the wellbore, may be applied to the non-spherical particulates as acoating layer or glazing material. Such layers are especially applicablewhere the non-spherical particulate is porous. The coating or glazing ispreferably applied to the circumference of the non-sphericalparticulates. The coating or glazed material may be used as a sealant toprevent entry of the carrier fluid or other wellbore fluids into thecore of the particulates. The amount of coating, when present, istypically from about 0.5 to about 10% by weight of the coatednon-spherical particulate.

The coating may be applied to the non-spherical particulates using anysuitable method known in the art. For example, the process, as disclosedin U.S. Pat. No. 7,135,231, may consist of heating the non-porousparticulates to a temperature between from about 93° C. to about 425°C., adding the heated particulates to a mixing apparatus, if necessary,and then applying a coupling agent, such as a polyamine, onto thesurface of the particulates. A resin coating may then be sputtered ontoat least a portion of the surface of the particulates. If additionalprotection is necessary, the process can include sputtering additionalresin coats onto the particulates in an incremental manner, such thatthe resultant coated particulate has a plurality of interleaved resincoats fully coating the particulates.

In another embodiment, the non-spherical particulates may be heated to atemperature between from about 93° C. to about 425° C. and a resinouscoating then applied while the particulates are being cooled.

Suitable coatings include phenolic resins, phenol-formaldehyde resins,melamine-formaldehyde resins, polyurethanes, carbamate resins, epoxyresins, polyamides, polyolefins, such as polyethylene, polystyrene and acombination thereof. In a preferred embodiment, the coating is an epoxyresin, phenol formaldehyde resin or a urethane resin.

A proppant pack composed at least in part of the non-sphericalparticulates discussed herein exhibit greater porosity than a proppantpack, of equivalent bulk volume having spherical particulates in placeof the non-spherical particulates. Further, the porosity of a proppantpack having a portion of spherical particulates substituted withnon-spherical particulates exhibits greater porosity at equivalent bulkvolumes. The porosity of a proppant pack containing non-sphericalparticulates defined herein may range from about 45 to about 75 percent,more typically in the range of from about 50 to about 60 percent.Consistent with the fact that the non-spherical particulates exhibitgreater porosity than spherical particulates, proppant packs containingnon-spherical particulates exhibit enhanced permeability at elevatedstresses.

In another embodiment, the non-spherical particulates are non-porous andare hollow. Such non-spherical particulates are capable of being atleast partially filled with a chemical treatment agent. For instance,the internal volume of the hollow cylindrical non-porous particulatesmay be up to about 70 percent by volume of the cylindrical proppant.

In another embodiment, the non-spherical particulates are non-porous andare hollow. Such non-spherical particulates are capable of being atleast partially filled with a chemical treatment agent. For instance,the internal volume of the hollow cylindrical non-porous particulatesmay be up to about 70 percent by volume of the cylindrical proppant.

When the non-spherical particulates are employed in deep waterenvironments having high closure stresses, the ASG of the non-sphericalparticulates is preferably between from about 1.0 to about 4.0. In suchapplications, fracturing may be conducted at closure stresses greaterthan about 1500 psi and at temperatures ranges between ambient and 260°C. As a result, the non-spherical particulates function well in ultradeep, hot, high closure stress applications.

For use in less harsh environments, the ASG of the non-sphericalparticulates is generally less than or equal to 2.0, generally betweenfrom about 1.05 to about 2.0.

The non-spherical particulates are generally introduced into thewellbore with a carrier fluid. Any carrier fluid suitable fortransporting the particulates into the wellbore and/or subterraneanformation fracture in communication therewith may be employed including,but not limited to, carrier fluids including a brine, salt water,unviscosified water, fresh water, potassium chloride solution, asaturated sodium chloride solution, liquid hydrocarbons, and/or a gassuch as nitrogen or carbon dioxide. In a preferred embodiment, thecarrier fluid is unviscosified water or brine.

The carrier fluid may be gelled, non-gelled or have a reduced or lightergelling requirement. The latter may be referred to as “weakly gelled”,i.e., having minimum sufficient polymer, thickening agent, such as aviscosifier, or friction reducer to achieve friction reduction whenpumped downhole (e.g., when pumped down tubing, work string, casing,coiled tubing, drill pipe, etc.), and/or may be characterized as havinga polymer or viscosifier concentration of from greater than 0 pounds ofpolymer per thousand gallons of base fluid to about 10 pounds of polymerper thousand gallons of base fluid, and/or as having a viscosity of fromabout 1 to about 10 centipoises. The non-gelled carrier fluid typicallycontains no polymer or viscosifer.

The use of a non-gelled carrier fluid eliminates a source of potentialpacking and/or formation damage and enhancement in the productivity ofthe well. Elimination of the need to formulate a complex suspension gelmay further mean a reduction in tubing friction pressures, particularlyin coiled tubing and in the amount of on-location mixing equipmentand/or mixing time requirements, as well as reduced costs. In oneembodiment employing a substantially neutrally buoyant particulate and abrine carrier fluid, mixing equipment need only include such equipmentthat is capable of (a) mixing the brine (dissolving soluble salts), and(b) homogeneously dispersing in the substantially neutrally buoyantparticulate.

The non-spherical particulates may be advantageously pre-suspended as asubstantially neutrally buoyant particulate and stored in the carrierfluid (e.g., brine of near or substantially equal density), and thenpumped or placed downhole as is, or diluted on the fly. The term“substantially neutrally buoyant” refers to non-spherical particulatesthat have an ASG sufficiently close to the ASG of the selected ungelledor weakly gelled carrier fluid (e.g., ungelled or weakly gelledcompletion brine, other aqueous-based fluid, slick water, or othersuitable fluid) which allows pumping and satisfactory placement of theparticulate using the selected ungelled or weakly gelled carrier fluid.

Suitable chemical treatment agents for at least partially filling thenon-spherical particulates are those which are water-soluble oroil-soluble. Further such chemical treatments agents may those which arecapable of being released into the formation by heat or mechanicalstress. Suitable materials for such non-porous particulates are ceramicsas well as organic polymeric materials, such as polyolefins.

Suitable chemical treatment agents include scale inhibitors, corrosioninhibitors, paraffin inhibitors, demulsifiers, gas hydrate inhibitors,flocculating agents, asphaltene dispersants as well as mixtures thereof.Scale inhibitors, corrosion inhibitors and paraffin inhibitors, such aswax crystal modifiers, have particular applicability with thenon-spherical particulates.

The composite of chemical treating agent and non-spherical particulatesmay be made by placing the non-spherical particulates in the desiredchemical treating agent and then allowing the chemical treatment agentto at least partially fill or enter the particulate either by capillaryaction or by the aid of a vacuum. An exemplary procedure is to place thenon-spherical particulate in a dilute solution of the chemical treatmentagent and allow the chemical treatment agent to fill the hollow innerarea of the particulate. The at least partially filled non-sphericalparticulate is then dried. The non-spherical particulates are thensieved through an appropriate mesh size screen to separate outindividual particulates.

Once the non-spherical particulates are placed into the fracture, thechemical treatment agent is slowly released as the oil and/or naturalgas passes around and through the non-spherical particulate. The rate ofrelease is based on the chemical treatment agent, the temperature of thewell, the flow rate of hydrocarbons, the percentage of water in theeffluent, etc. The chemical treatment agent slowly dissolves as in atime-release mechanism. Gradual dissolution of the chemical treatmentagent insures that the chemical treatment agent is available to thehydrocarbon for extended periods of time. As a result, the chemicaltreatment agent is available for chemical modification of the depositedmaterials contained in the produced fluids within the wellbore and/orsubterranean formation.

The following examples will illustrate the practice of the presentinvention in a preferred embodiment. Other embodiments within the scopeof the claims herein will be apparent to one skilled in the art fromconsideration of the specification and practice of the invention asdisclosed herein. It is intended that the specification, together withthe example, be considered exemplary only, with the scope and spirit ofthe invention being indicated by the claims which follow.

EXAMPLES Example 1

This Example illustrates changes in porosity in a birch wood proppantpack when at least a portion of spherical proppant of 12 to 13 mmdiameter was replaced with non-spherical proppant. The non-sphericalbirch wood was rod-shaped or cylindrical-shaped and had a diameterranging from about 9 mm to about 10 mm and was about 50 mm long.

The measured specific gravity of the birch wood (spheres and rods) was0.671 (+/−0.039) (compared to a specific gravity of birch of 0.670,reported in the literature). The bulk density of the two wood shapes wasdetermined by filling a measuring cylinder with the material to the 200ml mark. The bulk density, mass/volume, and porosity were thendetermined.

Spherical Birch

Bulk density of spheres=0.331 g/cc (+/−0.000)

Porosity=(1−0.331/0.670)×100=50.6%

Rod-Shaped Birch

Bulk Density of rods=0.229 g/cc (+/−0.006)

Porosity=(1−0.229/0.670)×100=65.8%

A 50:50 and 75:25 by weight mixture of spherical birch:rod-shaped birchwere then prepared and the bulk density of the mixtures were thendetermined as above.

50:50 Mixture

Bulk density=0.280 g/cc (+/−0.003)

Porosity=(1−0.280/0.670)×100=58.2%

75:25 Mixture

Bulk density=0.300 g/cc (+/−0.001)

Porosity=(1−0.300/0.670)×100=55.2%

These results demonstrate that the porosity of a proppant pack composedof rod-shaped proppant is greater than the porosity of a proppant packcomposed of spherical proppant. The results also demonstrate that theporosity of a spherical proppant pack may be increased by the additionof non-spherical proppant to the proppant pack. In this case, theporosity increased to 58.2% from 50.6% when 50 weight percent ofspherical proppant in the pack was replaced with rod-shaped proppant.The addition of 25 weight percent of rod-shaped proppant to thespherical proppant caused a porosity increase from 50.6% to 55.2%. Sincethe spheres and rods have the same specific gravity, the porosityincrease is the result of changes in the packing structure caused by thesubstitution of spherical-shaped proppant with rod-shaped proppant. Asparticles deviate from spherical to a more elongated shape, the packporosity of the resulting proppant pack increases. The Carmen-KozenyEquation relates permeability to porosity through pore geometricfactors, such as tortuosity and surface area. Since permeability is apower law function of porosity by this equation, even a small increasein porosity translates into a significant increase in permeability.

Example 2

This Example illustrates changes in porosity in a 20/40 bauxite proppantpack when at least a portion of ceramic proppant is replaced withaluminum needles. The aluminum needles were cylindrical and had adiameter ranging from about 0.5 mm to about 0.75 mm and were about 2 mmto 4 mm long.

The measured specific gravity of the bauxite proppant was 2.728(+/−0.005). The measured specific gravity of the uncoated aluminumneedles was 2.695 (+/−0.013). Bulk density was determined in accordancewith the procedure of Example 1 above.

20/40 Bauxite Ceramic

Bulk density=1.590 g/cc (+/−0.000)

Porosity=(1−1.590/2.728)×100=41.7%

Uncoated Aluminum Needles

Bulk Density=1.030 g/cc (+/−0.001)

Porosity=(1−1.030/2.695)×100=61.8%

A 50:50, 75:25 and 90:10 by weight mixture of 20/40 bauxiteceramic:uncoated aluminum needles were then prepared and the bulkdensity of the mixtures were then determined as above.

50:50 Mixture

Bulk Density=1.341 g/cc (+/−0.008)

Calculated specific gravity=2.711

Porosity=(1−1.341/2.711)×100=50.5%

75:25 Mixture

Bulk Density=1.469 g/cc (+/−0.001)

Calculated specific gravity=2.720

Porosity=(1−1.469/2.720)×100=46.0%

90:10 Mixture

Bulk Density=1.546 g/cc (+/−0.003)

Calculated specific gravity=2.725

Porosity=(1−1.546/2.725)×100=43.3%

These results demonstrate that the porosity of a proppant pack composedof uncoated aluminum needles is greater than the porosity of a proppantpack composed of only 20/40 bauxite ceramic. The results alsodemonstrate that the porosity of a 20/40 bauxite ceramic proppant packmay be increased by the addition of uncoated aluminum needles to theproppant pack; the greater the amount of uncoated aluminum needles inthe proppant pack, the greater the porosity of the proppant pack. Sincethe aluminum needles and the bauxite ceramic have almost the samespecific gravity, the porosity increase is the result from changes inthe packing structure caused by the substitution of the aluminumneedles. Since permeability is a power law function of the Carmen-KozenyEquation, even only a small amount of aluminum needles renders anincrease in porosity of the proppant pack and thus the permeability.

Example 3

Conductivity tests were performed according to a modified API RP 61(1^(st) Revision, Oct. 1, 1989) using an API conductivity cell with Ohiosandstone wafer inserts to simulate the producing formation. About 63 gof a multilayer pack of two types of ceramic rods (at 100%) were tested.Ceramic A consisted of cylindrical particulates ranging in diameter sizefrom about 0.75 mm to about 1.0 mm and about 2 to about 4 mm long.Ceramic B consisted of cylindrical particulates ranging in size fromabout 0.5 to about 0.75 mm and a length of from about 2 to about 4 mm.Also tested was a 85:15 by weight blend of the ceramic rods with a 20/40spherical ceramic proppant. A 100% pack of 20/40 spherical ceramicproppant was also tested for comparison. The conductivity cell was thenplaced on a press while stress was applied at 100 psi/minute until thetarget stress and temperature were reached. Fluid was then allowed toflow through the test pack maintaining Darcy flow. The differentialpressure was measured across 5 inches of the pack using a “ROSEMOUNT”differential pressure transducer (#3051C). Flow was measured usingMicromotion mass flow meters and data points were recorded every 2minutes for 50 hours. An Isco 260 D programmable pump applied andmaintained effective closure pressure. Experimental conditions were asfollows:

Temperature: 121° C.

Closure Pressure (psi): 1000-8000

Fluid pressure (psi): 300

Tables I and II illustrate the data for two types of 100% ceramic rodproppant packs. Table III represents data from a pack with a 85:15 blendof a typical 20/40 spherical ceramic proppant and one of the ceramicrods. Table IV represents the base line data for pack with 100% of the20/40 spherical ceramic proppant. Further, the conductivity andpermeability data are graphically displayed in FIG. 1 and FIG. 2,respectively.

TABLE I Long-Term Conductivity, 100% Ceramic A at 250° F. and 2 lb/ft.²TIME, STRESS, CONDUCTIVITY, PERMEABILITY, WIDTH, hours Psi mDft D mm 01000 19859 1047 5.78 50 1000 19333 1021 5.77 0 2000 14164 792 5.45 502000 12269 694 5.39 0 4000 5074 316 4.89 50 4000 3456 223 4.73 0 60001464 102 4.36 50 6000 844 62 4.16 0 8000 529 40 4.01 50 8000 240 19 3.86

TABLE II Long-Term Conductivity, 100% Ceramic B at 250° F. and 2 lb/ft.²TIME, STRESS CONDUCTIVITY PERMEABILITY WIDTH Hours psi mDft D mm 0 100011000 681 4.92 50 1000 10932 677 4.92 0 2000 8950 580 4.70 50 2000 7688503 4.66 0 4000 5782 404 4.36 50 4000 4404 314 4.28 0 6000 3056 228 4.0950 6000 2253 174 3.94 0 8000 1711 137 3.80 50 8000 1132 93 3.71

TABLE III Long-Term Conductivity. 15:85 Mixture of Ceramic B: 20/40Spherical Ceramic Proppant, 250° F. and 2 lb/ft.² TIME, STRESS,CONDUCTIVITY, PERMEABILITY, WIDTH, hours psi mDft D mm 0 1000 7082 4674.62 50 1000 6935 460 4.60 0 2000 5790 386 4.57 50 2000 5596 375 4.55 04000 5526 372 4.53 50 4000 4564 322 4.32 0 6000 4197 298 4.30 50 60003266 240 4.15 0 8000 3066 233 4.01 50 8000 2627 205 3.91 0 10000 2049165 3.78 50 10000 1770 147 3.68

TABLE IV Long-Term Conductivity, 100% 20/40 Spherical Ceramic Proppant,250° F. and 2 lb/ft.² CONDUC- TIME, STRESS TIVITY PERMEABILITY WIDTHHours psi mDft D mm 0 1000 5684 391 4.43 50 1000 5224 361 4.41 0 20005130 359 4.36 50 2000 5048 355 4.33 0 4000 4189 296 4.31 50 4000 4022295 4.16 0 6000 3805 281 4.13 50 6000 3033 231 4.01 0 8000 2620 207 3.8650 8000 2583 207 3.81 0 10000 2272 154 3.68 50 10000 1839 154 3.64

From the foregoing, it will be observed that numerous variations andmodifications may be effected without departing from the true spirit andscope of the novel concepts of the invention.

What is claimed is:
 1. A method of stimulating production ofhydrocarbons from a subterranean formation penetrated by a wellbore,comprising introducing into the wellbore a proppant of a non-sphericalceramic coated with a resin or a glazing material and forming a proppantpack in the formation, wherein the proppant pack comprises aclosed-packed structure of particulates of the proppant and furtherwherein the particulates of the proppant are in communication with eachother.
 2. The method of claim 1, wherein the non-spherical ceramic isporous.
 3. The method of claim 2, wherein the non-spherical ceramic iscoated with a resin which is permeable or semi-permeable to fluidsproduced from the wellbore.
 4. The method of claim 1, wherein thenon-spherical ceramic is non-porous.
 5. The method of claim 4, whereinthe non-spherical ceramic is coated with a resin which is permeable orsemi-permeable to fluids produced from the wellbore.
 6. The method ofclaim 1, wherein the non-spherical ceramic is composed of firedkaolinitic particles.
 7. The method of claim 1, wherein thenon-spherical ceramic is bauxite.
 8. The method of claim 1, wherein thenon-spherical ceramic is a natural ceramic.
 9. The method of claim 8,wherein the natural ceramic is selected from the group consisting ofvolcanic rocks, perlite and porous lavas and mixtures thereof.
 10. Themethod of claim 8, wherein the natural ceramic is pumice, HawaiianBasalt, Virginia Diabase, Utah Rhyolite or a mixture thereof.
 11. Themethod of claim 1, wherein the non-spherical ceramic is treated with aglazing material.
 12. The method of claim 1, wherein the non-sphericalceramic has an apparent specific gravity less than or equal to 2.0.